Use of dimethyl and diethyl adipates in vinylidene resins



2,859,197 Patented Nov. 4, 1958 USE OF DllVIETHYL AND DIETHYL ADTPATES IN VINYLIDENE RESINS Robert J. Reid, Canal Fulton, William Mayo Smith, Jr., Cuyahoga Falls, and Byron H. Werner, Akron, Ohio, assignors to The Firestone Tire & Rubber Company, Akron, Ohio, a corporation of Ohio Application February 23, 1954 Serial No. 412,075

8 Claims. (Cl. 260-313) No Drawing.

This invention relates to the use of dimethyl and diethyl adipates as processing. aids in the hot melt extrusion of crystalline polymers and copolymers of vinylidene chloride.

These crystalline polymeric resins have been known for some time. They have been used to a substantial extent in the manufacture of films and filaments for various purposes, but the extrusion has presented various difliculties. The high temperatures necessary for processing are very close to the decomposition temperature of the composition. Therefore, it is essential that some additive be used which will lower the processing temperature below the critical range without having any undesirable effect on the products obtained.

Such resins are characterized by crystalline behavior, i. e., they fuse sharply to form relatively fluid melts. n quenching and orienting, the extruded filaments and films are crystalline in character. A syndrome of this crystalline habit is the recalcitrance of these resins to compounding: The macromolecules of these resins prefer contact with each other and tend to reject any foreign substances such as plasticizers and the like. In the random structure obtained without orientation any added ingredient of limited compatibility, such as the processing aids of this invention, is retained in larger percentages than is possible in the stretched or oriented products. On stretching, the tendency toward exudation or spewing is considerably increased. In orienting films and filaments of vinylidene resins they are stretched to several times their original length, and ordinarily until there is a sharp rise in the modulus. It is diflicult to provide suitable processing aids which do not exhibit an undesirable spew or bloom on the surface. of the oriented products and which in addition possess good heat and light stability or which at least are'not detrimental to such stability.

Thus, the problem of providing processing aids for these crystalline resins is complicated not only by the fact that they tend to reject and spew the majority of conventional plasticizers, but, because the resins are extruded as hot melts at temperatures in the neighborhood of, for example, 170 C., many conventional resin-compounding ingredients tend to decompose or react with other compounding ingredients which are present when the resins are maintained in a molten state immediately prior to and during'extrusion. I

The crystalline resins to which the processing aids of this invention are added include both homopolymers "of vinylidene chloride and copolymers thereof with not more than substantially percent of other ethylenically unsaturated compounds copolymerizable therewith. The copolymers contain at least substantially 85 percent of vinylidene chloride. Suitable comonomers for the copolymerization include, for example, vinyl chloride, vinyl fluoride, vinyl acetate, styrene, acrylic and methacrylic esters such as methyl methacrylate, ethyl methacrylate, and the like, acrylonitrile, vinyl-type ethers'and ketones such as methylvinyl ether, methylvinyl ketone and related compounds such as methylisopropenyl ketone and the like. For a more complete list of compounds known to copolymerize with vinylidene chloride to produce resins which can be plasticized as herein described see Krczil, Kurzes Handbuch der Polymerisationstechnik, vol. II, Mehrstofipolymerization, Edwards Bros., Inc., p. 739, the items indented under vinylidene chlorid.

The processing aids of this invention are the dimethyl and diethyl adipates. They have excellent light stability and good heat stability as well as good spew resistance. They are non-toxic, non-allergic, and relatively odorless. In addition, they do not appreciably increase the tendency of oriented films or filaments to shrink when exposed to elevated temperatures.

Compounding and testing With regard to the .use of the processing aids, a small amount, in the range of 3 to 8 percent or up to 10 percent based on the weight of the resin will generally be found most satisfactory. Less than 3 percent may be used in admixture with another processing aid. Such percentages will be stably retained within the resin in the finished oriented article. In no case will more than about 10 percent of the processing aid be employed in a vinylidene resin because such larger amounts are incompatible and exude to the surface of oriented products produced from vinylidene polymeric resins containing 85 percent or more of vinylidene chloride.

The adipates of this invention can be employed with the epoxy heat stabilizers such as glycidyl-phenylether,

the mono-, di-, tri-, tetra-, and penta-chlorinated derivatives of phenoxypropene oxide, polymeric phenoxy compounds prepared from various dihydroxy phenols and epichlorhydrin, etc. Likewise, they can 'be employed with the light stabilizers which are esters of salicylic acid such as phenyl salicylate, 4-tert-butylphenyl salicylate, 4-octyl phenyl salicylate, 2-methyl phenyl salicylate, 4-chloro phenyl salicylate, 3-methyl phenyl salicylate, 4t-amyl phenyl salicylate, 4-nonyl phenyl salicylate, 2-octyl-4- methyl salicylate, 2-isopropyl salicylate, nonyl salicylate, ethylhexyl salicylate, n-butyl salicylate, etc.

The dimethyl and diethyl adipates impart desirable extrusion properties to the resins and are retained in the extruded, oriented products. They have no adverse effect on light or heat stability and many actually assist in their action.

Test data was compiled from compositions both with and without light and heat stabilizers according to the following formulation:

Parts by weight Crystalline resinous copolymer of vinylidene chloride and vinyl chloride (85:15) 100 Glycidyl phenyl ether 0 or 2 4-t-butyl phenyl salicylate 0 or 2 Processing aid 8 The additives were ball milled with the resin, and samples tested for heat stability, light stability and spew according to the methods given below:

Heat stability Five grams of the composition to be tested were charged into a compression mold of Hastelloy C (a 55/ 20/6/ 14/ 5 Ni/Mo/Fe/Cr/W alloy) in the form of a cylinder 1.25 inches in diameter. The molding cycle was-- (1) Beat for three minutes with steam at lbs./sq. in. and mold pressure of 1000 lbs/sq. 'in.;

(2) Water cool for two minutes under 1000 lbs/sq. in. mold pressure; and

(3) Eject from the'press.

The resultant cylindrical button (1.25 inches in diameter and .125.188 inch in height) was then cut into sectorshaped specimens which were placed in a forced-draft oven at C. Specimens were removed at intervals o10,.20,.and.30.n1inutes.after placing in the oven, and

the behavior of the specimens on the test as a whole plaque approximately 6to 8-niils-thick. The plaques were tested according to the-method of ASTM test 13620-451 under a sunlamp-for 240 hours.

'Plaques were also testedfinra weatherometer for 100 hours and-200 hours. -The weatherometer was a standard -X-i1-A-m-aehine,* using"a Corex D-filter and operating without the sprays.

.Spew rating A plaque of the compounded resin was pressed between Cellophane (regenerated cellulose) sheets .in a Carver press at 180 C.,' using approximately 1.5 grams of resin, 10:secondspreheat, and '15 seconds with the minimum pressure (pressure indicator just ofi zero). The plaque wasquenched in cold water immediately and an approximately %"inch wide strip was cut from the plaque, the cellophane removed, and the. strip oriented to its limit.

' The oriented strips were placed in glassine bags under mild pressure so that contact of the strips with the bag was'assured. Any exudation ofplasticizer could then be noted'as an oily stre'ak'on the 'glassine. Tests were carried out at room. temperature and at. 50 C., the latter condition tending to accentuate anymigration of plasticizer- In such atest, after 56 days at room temperature no spew was observed in samples containing the processing aids of this invention, whereas with dioctyl phthalate instead of anadipate, definitespew occurred after one day. 7

Test results -It 'was found that the use of'dimethyl and diethyl adipates do not adversely affect the heat and light stability of the resin compositions. In fact, it was observed that therde'letion of the glycidyl phenyl ether (used as'a heat stabilizer) and/or the 4-t-butyl phenyl salicylate (used as a light stabilizer) was partially compensated for by the processing aid. Adipate having only one or two carbonatoms in each alkyl group were chosen as processingaids because these materials do not show adverse spew under the aforementioned conditions. The light and'heat stability of these esters are entirely satisfactory. However, adipateshigher than diethyl showa markedly increased tendency to spew, and above the levels mentioned cannot be acceptably used.

The resins referred to herein are homopolymers of vinylidene chloride and copolymers thereof with up .to percent of other monomer copolymerized therewith; Increasing the vinyl chloride contentof a resin gives polymeric products in which plasticizer generally-.are-more compatible. The comment herein relative to spew is to be considered in the light of the fact that homopolymers of vinylidene chloride are somewhat less compatible with the processing aids than copolymers containing as much as 15 percent of vinyl chloride or other monomer.

Extrusion Tests were conducted using various processing aids 4 to 8 parts by weight of the processing aid, together with 2 parts glycidyl phenyl ether and 2 parts phenyl salicylate "as light andheat stabilizers. Theextrusions-were-carried out in conventional screw-type machines, the molten polyrner being forced through dies to form filaments which 7 were then quenched by passage through a water bath and cold-drawn some 400" percent by passage over diiferential speed rolls.

'With as little as four' parts ofdimeth'yl or diethyl adipate smooth filaments are produced readily in gauges from .006 inch to .015 inch without heat degrad'ation.

These filaments exhibit noexudation of adipate on -s'ton and possess excellent light stability when exposed to Florida sunshine. They have good heat stability. EX- trusions carried out with conventional plasticizers such as di-octylphthalate required at least 8 parts plasticizer to give desirable extrusion characteristics and such filaments on storage in all cases exuded the plasticizer.

T he adipates of this invention lower the melt temperature of the resin, allowingextrusions'to takeplace' without decomposition. 'The extruded products 'are smoothand of uniform diameter, and arefree of-spew 'after orientation. T

Whatwe claim is:

1. In the process of extruding and orienting a crystal line polymeric resin selected: fromthe groupconsistingof homopolymers of vinylidene chlor'ide'and --c0polymers thereof with up'to .15 percent by weight of other ethylejni cally unsaturated monomer,-the improvementwhich comprises extruding and orienting the molten resin whileadmixed with a dialkyl adipate, as 'a processingaidf the adipate being" from the-class consisting'pf the" dirtiethyl and diethyl adipates, whereby a=non exuding extruded, oriented product is obtained, the amount of the adipate being substantial but not inexcess of [about-" 10 percent, said percentages referring to percentagesby weighhof.

the polymeric resin.

2. The process of claim 1' in which the' dialkyl' adipate 1 'is dimethyl adipate.

3. The process of claimin which the dialkyl-adip'ate is diethyl adipate. V

4. The process of claim 1 in which an epoxy heat stabilizer and a light stabilizer are used in'the molten resin, the light stabilizer being an ester of salicylic; acid.

5. A resin composition which includes a crystalline polymeric resin selected from the group consistingot homopolymers of vinylidene chloride'-'and copol-ymers thereof with upto 15 percent by weight of other ethyleni- I cally unsaturated monomer, and'asa processingafaid a di-' 'alkyl adipate of the class consisting of'dimeth'yl a'dipate and diethyl adipate, the amount of the adipate being suo stantial but not in excess of'about 10 percent said' percentages-referring to-percentages by wei ghtfi'of the polymeric resin.

6. The resin composition of claim 5--in-which the sneeze-mes Citedtin'theifile of-thislpatent UNITED STATES rATEN-Ts 2,091,241 .Kvalnes -Aug."24,. 2,477,610 Irons 'Aug.- 2, 1 949 2,484,483 Berry Oct. 11, 1949 UNITED STATES PATENT OFFICE CERTIFICATION OF CORRECTION Patent No. 2,859 l97 November 4 Robert J. Reid et a1 It is hereby certified that error appears in the above numbered patent requiring correction and 'that the said Letters Patent should read as corrected below.

Column 4,, line 38 after "claim' insert 1 Signed and sealed this 10th day of April 1962.

(SEAL) V Attest:

ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents 

5. A RESIN COMPOSITION WHICH INCLUDES A CRYSTALLINE POLYMERIC RESIN SELECTED FROM THE GROUP CONSISTING OF HOMOPOLYMERS OF VINYLIDENE CHLORIDE AND COPOLYMERS THEREOF WITH UP TO 15 PERCENT BY WEIGHT OF OTHER ETHYLENICALLY UNSATURATED MONOMER, AND AS A PROCESSING AID A DIALKYL ADIPATE OF THE CLASS CONSISTING OF DIMETHYL ADIPATE AND DIETHYL ADIPATE, THE AMOUNT OF THE ADIPATE BEING SUBSTANTIAL BUT NOT IN EXCESS OF ABOUT 10 PERCENT, SAID PERCENTAGES REFERRING TO PERCENTAGES BY WEIGHT OF THE POLYMERIC RESIN. 